Resin composition

ABSTRACT

A water reducible resin composition, a water reducible admixture of such resin with solvents and plasticizers, a water reduced form of such mixture suitable for a coating, and a coating prepared from such water reduced mixture. Said resin is required to be prepared from a balance of hydrophobic enhancing and hydrophilic enhancing monomers. Generally such hydrophobic enhancing monomers are required to be a balance of monomers promoting hard and soft segments of the resin.

This is a division of application Ser. No. 827,196 filed Aug. 23, 1977,now U.S. Pat. No. 4,153,592, which was a division of Ser. No. 680,818,filed Apr. 28, 1976, now U.S. Pat. No. 4,064,092, which was acontinuation of Ser. No. 520,829, filed Nov. 4, 1974, now abandoned.

This invention relates to a particulate, water reducible resincomposition, a water reducible admixture of such resin with solvents andplasticizers, a water reduced form of such mixture suitable for acoating, and a coating prepared from such water reduced mixture. Thisinvention particularly relates to such materials utilizing a resinhaving a major portion derived from a balanced mixture of hydrophobicenhancing monomers and a minor portion derived from hydrophilicenhancing monomers.

Heretofore, various resins have been prepared and used for the purposeof providing various protective coatings. Exemplary of such resins arethose prepared by aqueous emulsion polymerizing monomer mixtures ofvarious materials such as minor or medium amounts of monomers such asstyrene and methyl methacrylate, and medium or major amounts of monomerssuch as 2-ethylhexyl acrylate and methacrylate acid. Generally suchresins are insoluble in water. Therefore, in general practice, resinsprepared from such monomers have either been dissolved in a suitableorganic solvent in order to provide a coating solution or have beendispersed in water with the aid of substantial emulsifying or surfactiveagents. Such water dispersions, when used to prepare coatings, generallyrequire additional hardeners to overcome residual emulsifiers andcuratives to crosslink the resin where water insoluble coatings aredesired. Otherwise, such coatings prepared from a water dispersion wouldsimply bleed away with a water wash.

A serious disadvantage of organic solvent solutions is their inherentpotential toxicity, flammability and environmental pollution. As aresult, a commercially useful water dispersion or solution is highlydesirable.

Therefore, it is an object of this invention to provide a resin formedby aqueous emulsion polymerization which can be conveniently dispersedor dissolved in an aqueous medium to form a suitable coatingcomposition.

In accordance with this present invention, a resin, suitable for a waterreducible composition, having a Ring and Ball softening point in therange of about 100° C. to about 300° C. is prepared by the method whichcomprises free radical aqueous emulsion polymerizing, in an aqueousmedium having a pH in the range of about 2 to about 7, free radicalorganic solution polymerizing a monomer mixture which comprises, basedon 100 weight percent of monomers (A) about 60 to about 95, preferablyabout 70 to about 85, weight percent of at least one hard segmenthydrophobic enhancing monomer selected from styrene, α-methyl styrene,acrylonitrile, vinyl toluene, methyl methacrylate, vinyl chloride andvinylidene chloride,

(B) about 0 to about 35, preferably about 15 to about 25, weight percentof at least one soft segment hydrophobic enhancing monomer selected fromat least one acrylate selected from methyl acrylate, ethyl acrylate,butyl acrylate, 2-ethylhexyl acrylate, laural acrylate, isodecylmethacrylate, butyl methacrylate, isobutyl methacrylate, at least onevinyl ether selected from ethyl, butyl, octyl, decyl and cetyl vinylether and/or at least one diene selected from 1,3-butadiene, isopreneand 2,3-dimethyl butadiene, provided that said dienes of monomer part(B) and said monomer part (A) vinyl chloride and vinylidene chloride arenot mixed together and copolymerized, and

(C) about 3 to 15, preferably about 3 to about 10, weight percent of atleast one hydrophilic enhancing organic acid selected from acrylic,methacrylic, fumaric, itaconic and maleic acid.

In further accordance with this invention, a water reducible compositioncomprises an admixture or solution of 100 parts by weight of said resinwith about 50 to about 100 parts by weight of coalescing, preferablywater soluble, solvent therefor generally selected from ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonobutyl ether, diethylene glycol monobutyl ether, diethylene glycolmonoethyl ether acetate, diethylene glycol diethyl ether, ethyleneglycol monomethyl ether acetate, methyl ethyl ketone, acetone, methylpropyl ketone and diacetone alcohol and about 5 to about 70 parts byweight of at least one resin-compatible plasticizer characterized by amelting point of about -40° C. to about 25° C., boiling point of atleast 95° C. and solubility parameter of about 8 to about 16.

In further accordance with this invention, a coating composition isprovided which is prepared by mixing and reacting sufficient amount of avolatile amine with said water reducible mixture and mixing with waterto form a stable dispersion or solution of said composition having a pHof about 8 to about 14, where said amine is selected from primary,secondary and tertiary amines having a melting point in the range ofabout -40° C. to about 25° C. and a boiling point in the range of about50° C. to about 150° C.

In further accordance with this invention, a substantially waterinsoluble coating is provided on a substrate having a thickness in therange of about 1 to about 40, preferably about 1 to about 5 milsprepared by applying said coating composition to a substrate surface anddrying the applied coating to remove said water, amine and coalescingsolvent.

Although the actual mechanism of the invention is not thoroughlyunderstood, it is believed that the unique result is caused by theformation of a resin having a balance of hydrophobic elements,preferably a particular balance of hard and soft hydrophobic elements,with a minor portion of hydrophilic elements which takes on aresemblance of a polymeric surfactant. Such a surfactant-directedpolymer then coacts with a combination of a coalescing solvent for theresin itself and compatible plasticizer. Indeed, the result is a waterreducible composition in which the expected amount of coalescing solventis substantially reduced by the plasticizer. Indeed, this is a mostimportant feature. It has even been found that some typicallyessentially nonsolvents such as normal mineral oil can be successfullyadmixed with some of the coactive composition of this invention and theresulting mixture water reduced or having the property of being waterreducible.

Another important benefit of the coactive water reducible composition ofthe resin is that water dispersion or solutions can generally be formedwithout the normally attendant requirement and problem of substantialamounts of surfactive or emulsifying agents, although such agents can beused, if desired. The problem typically involved with large amounts ofsuch materials is that they generally inhibit physical properties of acoating of the resin unless extra curatives and/or hardeners are used.

The substantial amounts of heretofore required surfactive agents havethus correspondingly typically required addition of hardeners orcuratives for the resin, for coating purposes. This is because, upondrying, the coating can contain residual amounts of the surfactant whichcan degrade both the coating's physical properties and water solubility.Without the hardeners and curatives, such a coating on the outside of abuilding structure would tend to wash off during the first rainstorm.

Thus, it is a particular feature of this invention that the uniquecombination of said resin with the required plasticizer facilitates thepreparation of a stable dispersion of the resin in water minimal use ofcoalescing solvent and further enables the preparation of asubstantially water insoluble coating of the coalesced resin.

In the practice of this invention, it is required that a major portionof the monomers are required to form a hard segment of a hydrophobicnature from monomers selected from styrene, α-methyl styrene,acrylonitrile, vinyl toluene, methyl methacrylate, vinyl chloride andvinylidene chloride. In further practice of this invention, it ispreferred and usually required that a substantial minor portion of themonomers form a relatively soft segment which is also hydrophobic innature selected from acrylate, vinyl ether and certain diene typemonomers. For the so-called soft, hydrophobic segment, generally thebutyl acrylate, 2-ethylhexyl acrylate and butyl vinyl ether monomers arepreferred.

Only a very minor amount of the hydrophilic enhancing organic acid isrequired or allowed, preferably about 3 to about 10 weight percent. Forhydrophilic enhancing segment, it is generally preferred that the acidis selected from acrylic and methacrylic acids and especially preferredthat only a minimal amount is used in order to provide only a minimalamount of carboxylation of the resin itself.

For the preparation of the resin of this invention, it is generallydesired that it be produced in an aqueous emulsion medium having a pH inthe range of about 2 to about 7. The pH can simply be adjusted with aninorganic base such as a base selected from sodium hydroxide, potassiumhydroxide and ammonium hydroxide. Such a polymerization is conducted bywell-known means such as with adequate stirring, general reactor andreaction control and usually at a temperature in the range of about 5°C. to about 80° C. It is understood that the typical surfactive agents,or emulsifiers, and free radical generating catalysts can be used. Theresin is also recovered from the emulsion by generally accepted methods,such as coagulation, evaporation and extrusion to yield a hard,particulate resin.

At this point, it would be expected that in order to provide a suitablecoating composition, either a solution of the resin or a typical wateremulsion or suspension would have to be prepared. Indeed, if desired,such methods can be used. However, the uniqueness of the discoveryyields a resin and a coactive resin composition system which actssomewhat as its own surfactant and is thus more easily water reduciblewith the inclusion of plasticizer and coalescing solvent, if needed.

In this regard, a film forming, water reducible composition is preparedusing a mixture of the resin with suitable coalescing solvent andplasticizer. It is preferred that such coalescing solvent is at leastwater miscible and even more preferably that it is water soluble. Of thevarious solvents which can be used, generally the ethylene glycolmonobutyl ether, ethylene glycol monoethyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether and diethyleneglycol monobutyl ether are preferred. It should be noted that thesolvent and plasticizer can be mixed directly with the resin in itswater emulsion or latex without its normal recovery in its dried form,in most instances, if desired. In such an operation, the composite wouldautomatically be in a water reduced form, when sufficient amine is used.

Of the various plasticizers, it is desired that one be selected which isliquid at room temperature such as 25° C. and have a sufficiently highboiling point, preferably at least 100° C., and even more preferably, atleast 150° C., so that they do not volatilize from the coatingcomposition when applied to a substrate. Indeed, the plasticizer shouldenhance the water insolubility of a dried coating of the coalescedresin. Further, the plasticizer, or mixture of plasticizers, must becharacterized by being compatible with the resin itself. For thischaracterization, a solubility parameter in the range of about 8 toabout 16 is required. Such solubility parameter is of the type describedin The Encyclopedia of Polymer Science and Technology, Volume 3, page854, 1965, John Wiley and Sons, Inc., which is simply determined by theequation

    δ=(ΣF)/V=ΣF/MW/d

where

δ=solubility parameter

ΣF =sum of the pertinent molar attraction constants of groups determinedby Small, P A [J Appl Chem 3, 71, (1953)]

V=Molar volume at 25° C.

MW=molecular weight

d=density at 25° C.

Various plasticizers can be used for this purpose. They can, forexample, be of the type listed in the Federation Series On CoatingsTechnology, Unit Twenty-two, entitled "Plasticizers," published April,1974, so long as they fulfill the melting point, boiling point andcompatibility requirements.

Representative of various plasticizers are cyclic plasticizers such asphosphoric acid esters, phthalic anhydride esters and trimellitic acidesters as well as N-cyclohexyl-p-toluene sulfonamide, dibenzyl sebacate,diethylene glycol dibenzoate, di-t-octylphenylether, dipropane dioldibenzoate, N-ethyl-p-toluene sulfonamide,isopropylidenediphenoxypropanol, alkylated naphthalene, polyethyleneglycol dibenzoate, o-p-toluene sulfonamide, trimethylpentanedioldibenzoate and trimethylpentanediol monoisobutyrate monobenzoate.

Representative of various acyclic plasticizers are adipic acid esters,azelaic acid esters, citric acid esters, acetylcitric acid esters,myristic acid esters, phosphoric acid esters, ricinoleic acid esters,acetylricinoleic acid esters, sebacic acid esters, stearic acid esters,epoxidized esters, as well as 1,4-butane diol dicaprylate, butoxyethylpelargonate di[(butoxyethoxy)ethoxy] methane, dibutyl tartrate,diethylene glycol dipelargonate, diiso-octyl diglycolate, isodecylnonanoate, tetraethylene glycol di(2-ethylbutyrate), triethylene glycoldi(2-ethylhexanoate), triethylene glycol dipelargonate and2,24-trimethyl-1,3-pentane diol diisobutyrate.

Additional various plasticizers, cyclic, acyclic, and otherwise, includechlorinated paraffins, hydrogenated terphenyls, substituted phenols,propylene glycols, polypropylene glycol esters, polyethylene glycolesters, melamines, epoxidized soya oils, melamines, liquid, hydrogenatedabietate esters, epoxytallate esters, alkyl phthalyl alkyl glycolates,sulfonamides, sebacate esters, aromatic epoxies, aliphatic epoxies,liquid poly(α-methyl styrene), maleate esters, mellitate esters,benzoates, benzyl esters, tartrates, succinates, isophthalates,orthophthalates, butyrates, fumarates, glutarates, dicaprylates,dibenzoates and dibenzyl esters. It is to be appreciated that relativelylow molecular weight polymers and copolymers derived from monoolefinscontaining 4 to 6 carbon atoms, mixtures of diolefins and monoolefinscontaining 4 to 6 carbon atoms as well as such hydrocarbons andhydrocarbon mixtures with styrene and/or α-methyl styrene can also beused.

The preferred esters are prepared from the reaction of carboxylic anddicarboxylic acids including fatty acids, such as the phthalic acids,benzoic acid, dibenzoic acid, adipic acid, sebacic acid, stearic acid,maleic acid, tartaric acid, succinic acid, butyric acid, fumaric acidand glutaric acid with hydrocarbon diols, preferably saturatedhydrocarbon diols, having about 7 to 13 carbon atoms.

Representative of various phosphoric acid esters are cresyl diphenylphosphate, tricresyl phosphate, dibutyl phenyl phosphate, diphenyl octylphosphate, methyl diphenyl phosphate, tributyl phosphate, triphenylphosphate, tri(2-butoxyethyl) phosphate, tri(2-chloroethyl) phosphate,tri-2(chloropropyl) phosphate and trioctyl phosphate.

Representative of various phthalic anhydride esters are butyl octylphthalate, butyl 2-ethylhexyl phthalate, butyl n-octyl phthalate,dibutyl phthalate, diethyl phthalate, diisodecyl phthalate, dimethylphthalate, dioctyl phthalates, di(2-ethylhexyl) phthalate, diiso-octylphthalate, di-tridecyl phthalate, n-hexyl n-decyl phthalate, n-octyln-decyl phthalate, alkyl benzyl phthalate, bis (4-methyl-1,2-pentyl)phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate,di(2-butoxyethyl) phthalate, dicyclohexyl isodecyl phthalate,dicyclohexyl phthalate, diethyl isophthalate, di n-heptyl phthalate,dihexyl phthalate, diisononyl phthalate, di(2-methoxyethyl) phthalate,dimethyl isophthalate, dinonyl phthalate, dioctyl phthalates, dicaprylphthalate, di(2-ethylhexyl) isophthalate, mixed dioctyl phthalates,diphenyl phthalate, 2-(ethylhexyl) isobutyl phthalate, butyl phthalylbutyl glycolate, ethyl (and methyl) phthalyl ethyl glycolate,polypropylene glycol bis(amyl) phthalate, hexyl isodecyl phthalate,isodecyl tridecyl phthalate and iso-octyl isodecyl phthalate.

Representative of trimellitic acid esters are triiso-octyl trimellitate,tri-n-octyl n-decyl trimellitate, trioctyl trimellitate,tri(2-ethylhexyl) trimellitate, tri-n-hexyl n-decyl trimellitate,tri-n-hexyl trimellitate, triisodecyl trimellitate and triisononyltrimellitate.

Representative of various adipic acid esters aredi[2-(2-butoxyethoxy)ethyl] adipate, di(2-ethylhexyl) adipate,diisodecyl adipate, dioctyl adipates (including diisooctyl adipate)n-hexyl n-decyl adipate, n-octyl n-decyl adipate, and di-n-heptyladipate.

Representative examples of sebacic acid esters are dibutyl sebacate,di(2-ethylhexyl) sebacate, dibutoxyethyl sebacate, diiso-octyl sebacateand diisopropyl sebacate.

Representative examples of azelaic acid esters are di(2-ethylhexyl)azelate, dicyclohexyl azelate, diisobutyl azelate and diiso-octylazelate.

In the practice of this invention, the water reducible composition ofresin, plasticizer and coalescing solvent, if used, is water reduced byneutralizing the carboxyl groups of the resin with a suitable amine andmixing with water. The resulting dispersion or solution can generally becharacterized by being stable without appreciable, if any, precipitationof the resin for a period of at least 30 days and preferably for aperiod of at least 365 days or more at about 25° C.

Various, relatively volatile, amines can be used for the purpose ofreacting with the carboxyl groups of the prepared resin. Representativeof various primary amines are ethyl amine, propyl amine, butyl amine,isoamyl amine, amyl amine, hexyl amine, heptyl amine and ethanol amine.Representative of various secondary amines are diethyl amine and ethylethanol amine and morpholine. Representative of various tertiary aminesare dimethylethanol amine, dimethyl amine and 2-methyl-1-aminopropanoland N-methyl morpholine.

Generally, for the purpose of this invention about 100 to about 400parts by weight water are used per 100 parts by weight neutralizedresin, although more or less water can usually be used depending onwhether a high or low viscosity dispersion or solution is desired orwhether a high or low solids content is desired. It also depends on thetype and amount of coalescing solvent and plasticizer used. The waterreduced coating composition, as an aqueous dispersion or solution, isapplied as a coating onto a suitable substrate surface such as wood,masonry, various plastics and various metals. The water, amine andcoalescing solvent are evaporated from the coating, usually at atemperature in the range of about 20° C. to about 100° C., preferablyabout 25° C. to about 50° C., to leave a substantially water insolublecoating of the coalesced resin and plasticizer. Generally such a coatingcan be prepared and applied without the need for additional hardeningagents or curatives to decrease the water sensitivity.

Therefore, it is an important feature of this invention that a durablecoating is formed on a substrate through the preparation of a particularresin having balanced hydrophilic and hydrophobic elements, preferablywith a further balance of hard and soft segments, and the formation of awater reduced composition of such resin with a combination of coalescingsolvent and compatible plasticizer.

The practice of the invention is more fully illustrated by reference tothe following examples which are intended to be illustrative rather thanlimiting of the scope of the invention. All parts are by weight unlessotherwise indicated.

EXAMPLE I

Various resins suitable for preparing water reducible compositions wereprepared by the following method and labeled herein as Experiments A-G.

To a reactor was charged water, suitable emulsifiers, freeradical-generating catalyst and sufficient amount of ammonium hydroxidewith potassium pyrophosphate to achieve a pH of about 3.1 to about 6.The mixture was adjusted to a temperature of about 30° C. With stirring,monomers were added to the mixture and allowed to polymerize at atemperature of about 45° C. for about 8 hours. The resulting latex wasthen coagulated and dried to form a particulate resin having a Ring andBall softening point within a range of about 100° C. to about 300° C.The Ring and Ball softening point is of the type determinable by ASTMMethod E28-58T.

In this example, various monomer mixtures were used which are summarizedin the following Table 1. The columns A-G represent Experiments A-G withtheir corresponding amounts of monomers in parts by weight.

                  TABLE 1                                                         ______________________________________                                        Monomers           A     B     C   D   E   F   G                              ______________________________________                                        A. Hard segment                                                               styrene            55    56    45  45  65  65  70                             α-methyl styrene                                                                           14    --    --  --  --  --  --                             acrylonitrile      --    --    25  --  --  --  --                             vinyl toluene      --    --    --  25  --  --  --                             methyl methacrylate                                                                              --    15    --  --  --  --  --                             B. Soft segment                                                               2-ethylhexyl acrylate                                                                            25    --    --  --  --  20  --                             butyl acrylate     --    25    --  25  25  --  25                             ethyl acrylate     --    --    25  --  --  --  --                             C. Hydrophilic enhancing monomer                                              acrylic acid       --    --    --  --  10  15  --                             methacrylate acid  6     4     5   5   --  --  5                              ______________________________________                                    

EXAMPLE II

Film forming water reducible coating compositions were prepared bymixing 100 parts of several of the various resins produced according toExample I with 60 parts coalescing solvent and 60 parts of variousindividual plasticizers. Generally the coalescing solvent could bevaried in the range of about 60-85 parts and the plasticizer could bevaried in the range of about 10-100 parts, depending somewhat on theamount of coalescing solvent used.

For the purpose of this example, the experiments here are labeled on anoverall basis as AA-GG to correspond with the resins A-G produced inExample I and demonstrated in Table 2. The plasticizers are representedTabular form and numbered 1-15. Thus, Table 2 actually represents 7times 15, or 105, individual experiments. The mixtures were prepared bymixing the materials at various temperatures in the range of about 25°C. to about 80° C. Usually, the mixtures were prepared by mixing for aperiod in the range of about 20 to about 60 minutes.

The tabulation of various coalescing solvents and plasticizers used aremore clearly shown in the following Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Coalescing Solvents and                                                       Plasticizers    AA BB CC DD EE FF GG                                          __________________________________________________________________________    A. Coalescing solvents                                                        ethylene glycol monoethyl ether                                                               -- 60 60 -- -- -- --                                          ethylene glycol monobutyl ether                                                               60 00 00 60 60 60 60                                          B. Plasticizers                                                               1. chlorinated paraffin (50%                                                  chlorine)       60 60 60 60 60 60 60                                          2. hydrogenated terphenyl                                                                     60 60 60 60 60 60 60                                          3. tributoxyethl phosphate                                                                    60 60 60 60 60 60 60                                          4. styrenated phenol                                                                          60 60 60 60 60 60 60                                          5. polypropylene glycol                                                       dibenzoate      60 60 60 60 60 60 60                                          6. tricresyl phosphate                                                                        60 60 60 60 60 60 60                                          7. diisooctyl adipate                                                                         60 60 60 60 60 60 60                                          8. butyl phthalyl butyl                                                       glycolate       60 60 60 60 60 60 60                                          9. N-ethyl toluene                                                            sulfonamides (mixed isomers)                                                                  60 60 60 60 60 60 60                                          10. diisooctyl sebacate                                                                       60 60 60 60 60 60 60                                          11. diisodecyl phthalate                                                                      60 60 60 60 60 60 60                                          12. triisodecyl mellitate                                                                     60 60 60 60 60 60 60                                          13. dipropyleneglycol                                                         dibenzoate      60 60 60 60 60 60 60                                          14. diisooctyl azelate                                                                        60 60 60 60 60 60 60                                          15. tri-2-ethylhexyl citrate                                                                  60 60 60 60 60 60 60                                          __________________________________________________________________________

EXAMPLE III

Various water reduced coating compositions were prepared by simplymixing various coating compositions with water, after sufficientdimethyl ethanol amine was added, to achieve a pH of the resulting waterdispersion or solution in the range of about 8 to about 14. The waterreduced compositions were formed by mixing about 330 parts water withthe amine neutralized compositions of Experiments AA to GG at atemperature in the range of about 25° C. to about 80° C. for a period ofabout 20 to about 60 minutes. Stable dispersions or solutions wereformed which were stable for a period of at least 30 days at about 25°C.

Coatings of water reduced compositions AA to GG were formed onsubstrates selected from glass, aluminum and steel having thicknesses inthe range of about 1 to about 3 mils which, upon drying to remove water,coalescing solvent and amine, were essentially impervious to water. Thefilms were formed by applying the coatings to the substrate and dryingthem at a temperature in the range of about 20° C. to about 80° C. forabout 8 to about 24 hours.

EXAMPLE IV

The utilization of plasticizers in this invention have uniquely made itpossible to use solvents which are not generally considered truesolvents for the resin itself. Representative of such typically nonsolvents are low aromatic mineral spirits containing a maximum of about20 volume percent aromatic content.

Exemplary of a water reduced clear coating composition utilizing a nonsolvent is one prepared by mixing 100 parts of resin G, 70 partschlorinated paraffin (50% chlorine) plasticizer and 60 parts mineralspirits. After mixing at a temperature of about 75° C. the mixture wasneutralized with 5 parts of dimethyl ethanol amine. To the neutralizedcomposition was mixed 330 parts of water which provided a stabledispersion of the coating composition. It is important to note in thiscase that mineral spirits by itself is not considered a solvent for theresin used in this example.

EXAMPLE V

A water reduced paint, containing various pigments, fillers andlevelers, was prepared from a coating composition of this invention. Itwas prepared from a pigment dispersion, identified herein as Part A, anda vehicle, identified herein as Part B. The recipe is more clearly shownin the following Table 3.

                  TABLE 3                                                         ______________________________________                                        Part A           Part B                                                       Pigment Dispersion                                                                             Vehicle                                                      ______________________________________                                        water        200     ethylene glycol                                          thickener    10      monobutyl ether  68                                      pigment wetting agent                                                                      5       pine oil          1                                      defoamer     2       chlorinated paraffin                                                                           30                                      chelating agent                                                                            5       hydrogenated terphenyl                                                                         30                                      titanium dioxide                                                                           50      dimethyl ethanol amine                                                                          5                                      calcium carbonate                                                                          300     resin G (from Example I)                                                                       100                                     amorphous silica                                                                           100                                                              water (add after                                                              pigment mixture is                                                                         130                                                              ground)                                                                       ______________________________________                                    

The paint preparation was prepared by slowly, with agitation,introducing Part A into Part B until inversion is complete. Withagitation, 30 parts of Perlite 68B was slowly added to the mixture. Thefinal paint composition (a high build texture paint) had a pigmentvolume concentration of 62.5 percent and a solids content of 62.8percent. The coalescing solvent/water volume ratio was 20/80. Thiscoating was applied to a cement-asbestos substrate at a thickness of 30mils wet. After 30 minutes, tap water was cascaded down the coated panelat a rate of about 2 gallons per minute for 8 hours. The coating did notsoften or wash off.

In these examples, it has been shown how, in the practice of thisinvention, suitable resins can be prepared, water reducible compositionscan be prepared with the resin and how a durable coating can be formedfrom the water reduced composition.

In the practice of this invention, it should be pointed out that whenpreparing the resin, the vinyl chloride and vinylidene chloride monomersare not utilized when it is desired to use one of the dienes in thepolymerization process. In other words, if it is desired that the resincontain units derived from vinyl chloride and/or vinylidene chloride,then the diene is not used and vice versa.

The examples of this specification have also shown the wide utility ofvarious organic plasticizers suitable for use with the combination ofresin, coalescing solvent and water. It should be pointed out that therequirement of the organic plasticizer that it have a boiling point ofat least about 95° C. generally refers to the plasticizers which boilabove 95° C. or, if they only reasonably boil under a reduced pressurein order to prevent them from alternatively degrading, then the 95° C.requirement is intended to relate to such organic plasticizers whichdegrade at a temperature greater than 95° C.

In the further description of this invention, it has been pointed outthat the basic resin can be prepared by aqueous emulsion polymerizationor by organic solvent solution polymerization of the monomers. Withregard to the preparation of the resin by solution polymerization, it isto be understood that the polymerization is to be conducted by methodsgenerally known to those having skill in the art. In suchpolymerizations, generally aromatic solvents such as benzene, tolueneand xylene are used, with xylene and toluene being preferred, along withproperly selected free radical catalysts which are soluble in thesolvents. As it is known, and if desired, some alcohols such asisopropanol as well as other similar alcohols can be mixed with theorganic solvent. Furthermore, for the purpose of preparing the resinthrough solution polymerization, various amounts of the hereinbeforecoalescing solvents can also be mixed with the aromatic solvents. When acoalescing solvent is used for this purpose, generally the overallsolvent contains about 15 to about 25 or 30 weight percent of suchcoalescing solvent.

While certain representative embodiments and details have been shown forthe purpose of illustrating this invention, it will be apparent to thosehaving skill in this art that certain changes and modifications may bemade therein without departing from the spirit or scope of theinvention.

What is claimed is:
 1. A resin, suitable for use in a water reduciblecomposition having a Ring and Ball softening point in the range of about100° C. to about 300° C. prepared by the method which comprises freeradical aqueous emulsion polymerizing, in an aqueous medium having a pHin the range of about 2 to about 7, or free radical organic solutionpolymerizing a monomer method which comprises, based on 100 weightpercent of monomers(A) about 60 to about 95 weight percent of at leastone hard segment hydrophobic enhancing monomer selected from styrene,α-methyl styrene, acrylonitrile, vinyl toluene, methyl methacrylate,vinyl chloride and vinylidene chloride, (B) about 0 to about 35 weightpercent of at least one soft segment hydrophobic enhancing monomerselected from at least one acrylate selected from methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate, laural acrylate,isodecyl methacrylate, butyl methacrylate, isobutyl methacrylate, atleast one vinyl ether selected from ethyl, butyl, octyl, decyl and cetylvinyl ether and/or at least one diene selected from 1,3-butadiene,isoprene and 2,3-dimethyl butadiene, provided that said dienes ofmonomer part (B) and said monomer part (A) vinyl chloride and vinylidenechloride are not mixed together and copolymerized, and (C) about 3 to 15weight percent of at least one hydrophilic enhancing organic acidselected from acrylic, methacrylic, fumaric, itaconic and maleic acid.2. The resin of claim 1 prepared by free radical emulsion polymerizing amonomer mixture which comprises(A) about 70 to about 85 weight percentof at least one hard segment hydrophobic enhancing monomer selected fromstyrene, α-methyl styrene, acrylonitrile, vinyl toluene and methylmethacrylate, (B) about 15 to about 25 weight percent of at least onesoft segment hydrophobic enhancing monomer selected from at least oneacrylate selected from methyl acrylate, ethyl acrylate, butyl acrylate,2-ethylhexyl acrylate, laural acrylate, isodecyl methacrylate, butylmethacrylate and isobutyl methacrylate, and (C) about 3 to about 10weight percent of at least one hydrophilic enhancing organic acidselected from acrylic and methacrylic acid.